EP0862942A2 - Procédé de production d'eau desionisée - Google Patents

Procédé de production d'eau desionisée Download PDF

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Publication number
EP0862942A2
EP0862942A2 EP98103390A EP98103390A EP0862942A2 EP 0862942 A2 EP0862942 A2 EP 0862942A2 EP 98103390 A EP98103390 A EP 98103390A EP 98103390 A EP98103390 A EP 98103390A EP 0862942 A2 EP0862942 A2 EP 0862942A2
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EP
European Patent Office
Prior art keywords
demineralizing
compartments
pressure
ion exchange
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98103390A
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German (de)
English (en)
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EP0862942B1 (fr
EP0862942A3 (fr
Inventor
Ichiro Asahi Glass Company Ltd. TERADA
Hiroshi Asahi Glass Company Ltd. Toda
Kazuo Asahi Glass Company Ltd. Umemura
Mark Philip Huehnergard
David Florian Tessier
Ian Glenn Towe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GE Water Technologies Inc
AGC Inc
Original Assignee
Glegg Water Conditioning Inc
Asahi Glass Co Ltd
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Publication of EP0862942A2 publication Critical patent/EP0862942A2/fr
Publication of EP0862942A3 publication Critical patent/EP0862942A3/fr
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Publication of EP0862942B1 publication Critical patent/EP0862942B1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/4604—Treatment of water, waste water, or sewage by electrochemical methods for desalination of seawater or brackish water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis

Definitions

  • the present invention relates to an apparatus for producing deionized water, comprising an electrodialyzer having cation exchange membranes and anion exchange membranes alternately arranged to form demineralizing compartments and concentrating compartments and having ion exchangers accommodated in the demineralizing compartments, and designed to apply a voltage while supplying water to be treated to the demineralizing compartments.
  • an apparatus for producing deionized water it is common to obtain deionized water by passing water to be treated through a bed packed with an ion exchange resin so that impurity ions are removed as adsorbed on the ion exchange resin.
  • This apparatus comprises an electrodialyzer having anion exchange membranes and cation exchange membranes alternately arranged to form demineralising compartments and concentrating compartments and having ion exchangers accommodated in the demineralizing compartments, and is designed to apply a voltage while supplying water to be treated to the demineralizing compartments to carry out electrodialysis to produce deionized water.
  • this conventional apparatus various developments or improvements have already been made.
  • JP-A-61-107906 an apparatus designed to permit water to be treated to pass at least twice through demineralizing compartments of a deionizing apparatus
  • JP-A-1-307410 an apparatus designed to permit water to be treated to pass at least twice through demineralizing compartments of a deionizing apparatus
  • anion exchange resins are used as ion exchange resins to be packed in a portion where the water to be treated passes firstly
  • Ion exchange membranes to be used in such conventional apparatus for producing deionised water were in a wet state and accordingly difficult to handle at the time of setting (or incorporating) in an electrodialyzer, and they had a drawback that they tend to shrink as they are gradually dried during the setting.
  • the problem can not be solved simply by attempting to set the membranes in a dry state without any elaboration.
  • the ion exchange membranes will be in contact with wet state ion exchange resins present adjacent thereto, whereby the ion exchange membranes will be wetted, and the above mentioned problem of difficulty in handling wet membranes can not be solved.
  • the membranes will deform due to swelling when water is supplied to the electrodialyzer, whereby defects such as creases are likely to form on the membranes. Also from this viewpoint, the merits in setting the membranes in a dry state have been negated.
  • the present invention provides an apparatus for producing deionized water, comprising an electrodialyzer having cation exchange membranes and anion exchange membranes alternately arranged to form demineralizing compartments and concentrating compartments and having ion exchangers accommodated in the demineralizing compartments, and designed to conduct an electric current while supplying water to be treated to the demineralizing compartments, wherein a spacer is arranged in each concentrating compartment to maintain the thickness of the concentrating compartment, and the cation exchange membranes or the anion exchange membranes are incorporated in their dry state in the electrodialyzer, whereby water is supplied to the electrodialyzer, while each ion exchange membrane is brought in contact with the spacer by a pressure from the demineralizing compartment side.
  • the dry state of cation exchange membranes and/or anion exchange membranes to be incorporated in the electrodialyzer is preferably such that the water content is at most 10 wt%. If the water content exceeds 10 wt%, the dimensional change of the membranes due to a change in the external environment, particularly due to the change in humidity, tends to be substantial, such being undesirable.
  • the water content is particularly preferably from 0.5 to 8 wt%, whereby there will be no substantial dimensional change due to a change in humidity.
  • the pressure from the demineralizing compartment side which is used in the present invention to bring each ion exchange membrane in contact with the spacer arranged in each concentrating compartment by the pressure from the demineralizing compartment side is preferably from 0.1 to 10 kg/cm 2 . If the pressure is less than 0.1 kg/cm 2 , the membrane may not closely contact the spacer, whereby deformation by swelling of the membrane can not suppressed, such being undesirable. If the pressure is larger than 10 kg/cm 2 , the membrane and the spacer are likely to undergo physical deformation by the pressure, such being undesirable.
  • the pressure is particularly preferably from 0.5 to 5 kg/cm 2 , whereby deformation by swelling of the membrane can adequately be controlled, and no deformation of the membrane or the spacer will be brought about by the pressure, whereby the performance will be stable.
  • a means to create the pressure from the demineralizing compartment side in the electrodialyzer in order to bring the ion exchange membrane in contact with the spacer it is preferred to employ either (1) a means wherein the ion exchangers are packed in their dry state in the demineralizing compartments, and water is supplied to the electrodialyzer to let the ion exchangers swell to produce the pressure, (2) a means wherein the thickness of each demineralizing compartment is reduced by mechanical pressure so as to create the pressure due to the volume reduction of the demineralizing compartment, or (3) a means wherein the water pressure in the demineralizing compartments is made higher than the water pressure in the concentrating compartments to create the pressure.
  • the above means (1) wherein the ion exchangers are packed in their dry state in the demineralizing compartments is most preferred, since it is simple and effective.
  • the water content of the ion exchangers in their dry state is preferably at most 15 wt%. If the water content exceeds 15 wt%, when the ion exchangers are brought in contact with the ion exchange membranes in their dry state, the ion exchange membranes will be swelled, thus leading to a dimensional change, such being undesirable.
  • a frame which is compression-deformable by mechanical pressure may be employed, or a sheet which is compression-deformable by mechanical pressure, may be inserted between the membrane and the compartment frame for each demineralizing compartment.
  • the spacer to be arranged in each concentrating compartment of the electrodialyzer is preferably in the form of a net, such as a woven or non-woven fabric made of a plastic, and its structure is preferably such that the string diameter is from 0.1 to 2 mm, and the pitch is from 1 to 10 mm.
  • the pitch is the distance between diagonal points of a rhomb, square or rectangle of an opening in the net (the distance between the centers of strings). If the string diameter is smaller than 0.1 mm, the strength of the net tends to be low, such being undesirable.
  • the spacer is not limited to a net, and its structure may be any structure so long as it is thereby possible to maintain the predetermined space i.e. thickness for the concentrating compartment and to minimize the shielding of the electric current.
  • ion exchange membranes to be used in the present invention it is, of course, possible to use homogeneous ion exchange membranes.
  • they are preferably heterogeneous ion exchange membranes composed of ion exchange resin particles and a binder polymer.
  • a method for producing such heterogeneous ion exchange membranes a method is preferably employed in which an ion exchange resin of a powder particle form and a binder polymer are mixed and kneaded under heating, followed by heat extrusion molding to form a sheet.
  • the particle sizes of ion exchange resin particles are preferably such that the maximum particle size is at most 150 ⁇ m, those having particle sizes of from 100 to 150 ⁇ m are at most 5 wt% of the entire ion exchange resin particle material, and those having particle sizes of at most 20 ⁇ m are at most 20 wt%.
  • the maximum particle size exceeds 150 ⁇ m, or if those having particle sizes of from 100 to 150 ⁇ m exceed 5 wt%, pin holes are likely to form in heterogeneous ion exchange membranes thereby molded, or the mechanical strength of such membranes tends to be low, such being undesirable. If ion exchange resin particles having particle sizes of at most 20 ⁇ m exceed 20 wt%, the surface area of the ion exchange resin particles tends to remarkably increase, and kneading with the binder polymer tends to be inadequate, whereby defects tend to form, such being undesirable.
  • the binder polymer for the heterogeneous ion exchange membranes may, for example, be low density polyethylene, linear low density polyethylene, ultrahigh molecular weight high density polyethylene, high density polyethylene, polypropylene or a mixture thereof with a flexible rubber material.
  • a mixture of low density polyethylene with a rubber consisting one or both of ethylene-propylene rubber and ethylene-propylene-diene rubber is a particularly preferred polymer from the viewpoint of the elongation, flexibility and the strength of the resulting ion exchange membranes.
  • the content of the ethylene-propylene rubber or the ethylene-propylene-diene rubber in the mixture of low density polyethylene with ethylene-propylene rubber or ethylene-propylene-diene rubber is preferably from 10 to 50 wt%. If the rubber content is less than 10 wt%, the resulting membranes tend to be brittle, and if it exceeds 50 wt%, the membranes tend to be soft and weak against deformation by pressure, such being undesirable.
  • the rubber content is particularly preferably from 25 to 35 wt%, whereby a binder polymer excellent in the above mentioned physical properties will be obtained, and its molding will be easy.
  • polymer may be blended to the mixture of low density polyethylene with ethylene-propylene rubber or ethylene-propylene-diene rubber, for use as a binder polymer.
  • the polymer to be blended is preferably a polyhydrocarbon olefin such as high density polyetylene, ultrahigh molecular weight high density polyethylene, polypropylene or polyisobutylene.
  • the blend ratio of the pulverized ion exchange resin particles to the binder polymer is preferably such that the weight ratio of ion exchange resin/binder polymer is from 40/60 to 70/30.
  • the ion exchange resin is less than 40 wt%, the electric resistance of the resulting heterogeneous ion exchange membranes tends to remarkably increase, such being undesirable. If the ion exchange resin exceeds 70 wt%, the mechanical strength tends to be low, and molding tends to be difficult.
  • the ion exchangers to be accommodated in the demineralizing compartments of the electrodialyzer may, for example, be a dried ion exchange resin, or in the form of a porous ion exchanger prepared by molding an ion exchange resin into a sheet by means of a binder polymer.
  • the dried ion exchange resin and the binder polymer may be heated and mixed, or the binder polymer may be dissolved in a solvent and then mixed with the ion exchange resin, followed by removal of the solvent.
  • the ion exchanger molded into a sheet is efficient in handling, its packing is easy, and contact of the ion exchange resin particles in itself is good, whereby the electric resistance will be low, and thus, it is an ion exchanger suitable for use in the present invention.
  • the porosity of the porous ion exchanger is preferably at least 5 volume % as the proportion of continuous pores relating to permeation of the liquid. If the porosity is smaller than 5 volume %, the flow rate of the liquid decreases, and the pressure loss increases, such being undesirable.
  • the porosity is particularly preferably from 10 to 40%, whereby the water permeation is good, the demineralizing performance is excellent, and treated water of high purity can be obtained. This porosity is a value as the porous sheet is accommodated in a demineralizing compartment and is being used.
  • the porous ion exchanger may be formed of cation exchange resin particles, anion exchange resin particles, or a mixture thereof, or it may have a structure in which domains of cation exchange resin particles and domains of anion exchange resin particles are phase-separated in a sea-island pattern.
  • the ratio of the cation exchange resin particles to the anion exchange resin particles to be used is preferably such that the total ion exchange capacity ratio of cation exchange resin/anion exchange resin is from 30/70 to 80/20. If the total ion exchange capacity ratio is outside this range, the purity of treated water tends to be low, such being undesirable.
  • the weight proportion of the binder polymer used for the porous ion exchanger is preferably at most 20% relative to the total weight of the porous ion exchanger. If the weight proportion is larger than 20%, the binder polymer is likely to cover the surface of the ion exchange resin particles, whereby the adsorbing ability tends to be low, and the porosity tends to be low, whereby the flow rate of the liquid to be treated tends to decrease, and the pressure loss tends to increase, such being undesirable.
  • the weight ratio of the binder polymer is particularly preferably from 1 to 5%.
  • thermoplastic polymer a thermoplastic polymer or a solvent-soluble polymer is preferred from the viewpoint of the process for producing the porous ion exchanger.
  • a binder polymer the following is preferably employed.
  • the thermoplastic polymer low density polyethylene, linear low density polyethylene, ultrahigh molecular weight high density polyethylene, polypropylene, polyisobutylene, polyvinyl acetate, or an ethylene-vinyl acetate copolymer, may, for example, be mentioned.
  • solvent-soluble polymer natural rubber, butyl rubber, polyisoprene, polychloroprene, styrene-butadiene rubber, nitrile rubber, or a vinyl chloride-fatty acid vinylester copolymer, may, for example, be mentioned.
  • the thickness of the porous ion exchanger sheet having the ion exchange resin bound by the binder polymer is preferably from 1 to 300 mm. If the thickness is thinner than 1 mm, the thickness of the emineralizing compartment accommodating it will also be very thin. Consequently, water tends to hardly flow, whereby the amount of water treated tends to be small, such being undesirable. If the thickness exceeds 300 mm, the electric resistance tends to be high, such being undesirable.
  • the thickness of the ion exchange resin sheet is more preferably from 3 to 50 mm. This thickness is a value as the porous sheet is accommodated in a demineralizing compartment and is being used.
  • the electrodialyzer comprises a plurality of cation exchange membranes and anion exchange membranes alternately arranged, preferably via compartment frames, between an anode compartment provided with an anode and a cathode compartment provided with a cathode.
  • the cation exchange membranes and the anion exchange membranes are incorporated in their dry state.
  • the ion exchangers to be accommodated in the demineralizing components are in the form of sheets, such ion exchanger sheets are inserted between the ion exchange membranes.
  • demineralizing compartments each defined by an anion exchange membrane on the anode side and by a cation exchange membrane on the cathode side
  • concentrating compartments each defined by a cation exchange membrane on the anode side and by an anion exchange membrane on the cathode side
  • the thicknesses of the compartment frames of the demineralizing compartments and the concentrating compartments may not necessarily be the same.
  • the ion exchange membranes may be of a homogeneous type or a heterogeneous type, and in order to increase the mechanical strength, the one reinforced by a woven fabric or a non-woven fabric, may be used.
  • a spacer of a net form it is preferred to insert a spacer of a net form in order to maintain its thickness to a predetermined level. If ion exchangers are not yet accommodated in the demineralizing compartments of the electrodialyzer thus assembled, granular ion exchangers will be incorporated at this stage.
  • the ion exchange membranes of the electrodialyzer are permitted to swell by both waters to bring the ion exchange membranes in contact with the spacers and thereby to set them in a steady state, whereupon by conducting an electric current, demineralization of the water to be treated, can be carried out. It is also possible that without supplying the water to be treated from the beginning, a liquid which is preferably similar to the water to be treated, may be supplied to preliminarily swell and set the ion exchange membranes and the ion exchangers accommodated in the demineralizing compartments.
  • a voltage of from 4 to 20 V is applied to each unit cell to conduct an electric current preferably at a current density of from 0.00001 to 0.05 A/cm 2 .
  • FIG. 1 is a view which schematically illustrates an embodiment of the electrodialyzer of such a type.
  • A is an anion exchange membrane
  • K is a cation exchange membrane.
  • the anion exchange membranes A and the cation exchange membranes K are arranged in the electrodialyzer 1 via demineralizing compartment frames D 1 , D 2 , D 3 ⁇ D n and concentrating compartment frames C 1 , C 2 , C 3 ⁇ C n at predetermined distances, to form an anode compartment 2, concentrating compartments S 1 , S 2 ⁇ S n , demineralizing compartments R 1 , R 2 ⁇ R n and a cathode compartment 3.
  • reference numeral 4 indicates an anode
  • numeral 5 indicates a cathode.
  • a predetermined voltage is applied across the two electrodes during the operation, whereby anion components in the liquid to be treated which is introduced into the demineralizing compartments R 1 , R 2 ⁇ R n from a conduit 6, will permeate and move to the concentrating compartments on the anode side through the anion exchange membranes A, while cation components in the liquid to be treated will permeate and move to the concentrating compartments on the cathode side through the cation exchange membranes K, and the liquid to be treated itself will be deionized and discharged via a conduit 7.
  • water or a concentrating liquid is introduced into the respective concentrating compartments S 1 , S 2 ⁇ S n from a conduit 8, and the anion and cation components permeated and moved as described above, will be collected and discharged as a concentrated solution from a conduit 9.
  • Cations in the water to be treated which are captured by the cation exchangers in the demineralizing compartments, will have a driving force given by the electric field, will reach the cation exchange membranes via cation exchangers which are in contact with the cation exchangers which captured the cations, and further, they will pass through the membranes and move to the concentrating compartments.
  • anions in the water to be treated which are captured by the anion exchangers will move to the concentrating compartments via anion exchangers and the anion exchange membranes.
  • the cation exchangers and the anion exchangers are, respectively, gathered to form domains or gathered regions, whereby contact points of exchanger particles of the same ion type increase remarkably, so that movement of ions is facilitated, and the deionization performance will be improved.
  • binder polymer 70 wt% of low density polyethylene and 30 wt% of ethylene-propylene-diene rubber were mixed and kneaded by a laboplasto mill at 150°C for 30 minutes to obtain a mixture.
  • Diaion SK-1B styrene-divinylbenzene copolymer resin, ion exchange groups: -SO 3 Na type, apparent density: 0.825 g/ml, water content: 43 - 50 wt%, ion exchange capacity: 2.0 meq/ml
  • Mitsubishi Chemical Corporation which is a strongly acidic cation exchange resin, was used, and it was dried in hot air at 60°C for 24 hours and then pulverized by a jet mill.
  • the pulverized particles were sieved by a stainless steel meshed sieve to remove particles having particle sizes exceeding 150 ⁇ m.
  • the particle size distribution of the particles of the obtained ion exchange resin powder having particle sizes of at most 150 ⁇ m was measured by sieving, whereby those having particle sizes of from 100 to 150 ⁇ m were 1.2 wt%, and particles having particle sizes of at most 20 ⁇ m were 12 wt%.
  • Such ion exchange particles and the above mentioned low density polyethylene/ethylene-propylene-diene rubber mixture were mixed in a blend ratio of 60/40 (weight ratio), followed by kneading by a laboplasto mill at 130°C at 50 rpm for 20 minutes.
  • the obtained kneaded product was heat-melt pressed at 160°C by a flat plate press to obtain a cation exchange membrane having a thickness of 500 ⁇ m.
  • the obtained membrane had a breaking strength of 2.8 MPa, a breaking elongation of 160% and a burst strength of 0.15 MPa.
  • the water content in its dry state was 2.4 wt%, and the dimensional change when wetted, was 115%, relative to 100% in its dry state.
  • an anion exchange membrane having a thickness of 500 ⁇ m was prepared by using Diaion SA-10A (styrene-divinylbenzene copolymer resin, ion exchange groups: -N(CH 3 ) 3 Cl type, apparent density: 0.685 g/ml, water content: 43 - 47 wt%, ion exchange capacity: 1.3 meq/ml) manufactured by Mitsubishi Chemical Corporation, which is a strongly basic anion exchange resin, as an ion exchange resin.
  • Diaion SA-10A styrene-divinylbenzene copolymer resin, ion exchange groups: -N(CH 3 ) 3 Cl type, apparent density: 0.685 g/ml, water content: 43 - 47 wt%, ion exchange capacity: 1.3 meq/ml
  • the particle size distribution of particles of the ion exchange resin powder having particle sizes of at most 150 ⁇ m was such that those having particle sizes of from 100 to 150 ⁇ m were 0.9 wt%, and particles having particle sizes of at most 20 ⁇ m were 8 wt%.
  • the obtained membrane In its wet state, the obtained membrane had a breaking strength of 2.5 MPa, a breaking elongation of 150% and a burst strength of 0.13 MPa. Further, the water content in its dry state was 2.2 wt%, and the dimensional change when wetted, was 112%, relative to 100% in its dry state.
  • a linear low density polyethylene (Affinity SM-1300, tradename, manufactured by Dow Chemical Company) was mixed, followed by kneading at a temperature of from 120 to 130°C.
  • the obtained kneaded product was heat-molded at 130°C by a flat plate press to obtain a porous ion exchanger sheet having a thickness of 0.6 cm.
  • the porosity of continuous pores of this porous sheet was 23 volume %, and the water content was 2.5 wt%.
  • each demineralizing compartment of the electrodialyzer was 8 mm.
  • the spacer net (openings: rhomb) disposed in each concentrating compartment was made of polypropylene and had a string diameter of 0.5 mm, a pitch of 3 mm (the distance between the centers of strings located at the diagonal points) and a thickness of 1.2 mm at the crossing point of strings, and the thickness of each concentrating compartment frame was 1.2 mm. Further, the packing volume proportion of the porous ion exchange sheet in its dry state in each demineralizing compartment was 54%.
  • Water having an electroconductivity of 5 ⁇ S/cm was supplied for 10 minutes to the demineralizing compartments, the concentrating compartments and both electrode compartments of the electrodialyzer, followed by conducting an electric current for 15 hours for pretreatment to sufficiently wet the ion exchange membranes and the porous ion exchangers, whereupon production of deionized water was carried out.
  • Water having an electroconductivity of 5 ⁇ S/cm was used as the water to be treated, and demineralization was carried out by applying a voltage of 4 V per unit cell, whereby pure water having an electroconductivity of 0.06 ⁇ S/cm was constantly obtained at a production rate of 0.45 m 3 /hr.
  • the ion exchange membranes were taken out, and their state was inspected, whereby they were found as pressed against the spacer nets without creasing, and their sizes immediately after being disassembled, were 103% of the dry state in the case of the cation exchange membranes, and 102% of the dry state in the case of the anion exchange membranes. Thus, the dimensional changes were found to be suppressed. Further, the porous ion exchange sheets in the demineralizing compartments were taken out, and their volumes were measured and found to be 121% of the volumes of the demineralizing compartments.
  • An ion exchanger 15 in a dry state as a test sample is put into a metal container 10 of a rectangular parallelopiped, and a metal plate 11 is placed thereon, whereupon the position of a load cell 14 is adjusted so that the forward end of the load cell 14 will contact the metal plate 11 when the ion exchanger 15 swells to a thickness equal to the thickness of the demineralizing compartment (8 mm in the case of Examples).
  • the position of the load cell is set so that when the ion exchanger 15 is in a dry state, the sum of the distance between the forward end of the load cell 14 and the metal plate 11 and the thickness of the ion exchanger 15 will be equal to the thickness of the demineralizing compartment (8 mm in the case of Examples).
  • water is supplied from a water supply inlet 12, and from a load exerted to the load cell 14 when absorption of water reaches equilibrium, the pressure between the ion exchanger 15 and the metal plate 11 is obtained.
  • Example 2 A test was carried out in the same manner as in Example 1 except that as an ion exchanger packed in the demineralizing compartments, a dry mixture of a sodium sulfonate type cation exchange resin (Diaion SK-1B, tradename, manufactured by Mitsubishi Chemical Corporation) having a particle size of from 400 to 600 ⁇ m and an ion exchange capacity of 4.5 meq/g dry resin and a quaternary ammonium salt type anion exchange resin (Diaion SA-10A, tradename, manufactured by Mitsubishi Chemical Corporation) having a particle size of from 400 to 600 ⁇ m and an ion exchange capacity of 3.5 meq/g dry resin, was used, and the structure of the demineralizing compartments was modified to a structure capable of preventing flowing out of the granular ion exchange resins.
  • a dry mixture of a sodium sulfonate type cation exchange resin (Diaion SK-1B, tradename, manufactured by Mitsubishi Chemical Corporation) having a particle size of from 400 to 600 ⁇
  • the water content of the dry mixture was 8 wt%, and the blend ratio of cation exchange resin/anion exchange resin was 44/56 (weight ratio in dry state), and the ion exchange capacity ratio was 50/50.
  • the dry ion exchange resin mixture was packed into the demineralizing compartments at a volume packing proportion of 55%.
  • Example 2 In the same manner as in Example 1, the ion exchange membranes and the ion exchange resins were thoroughly wetted by supplying water for 10 minutes to the respective compartments of the electrodialyzer and the pretreatment by conducting an electric current for 15 hours, and then a test for producing deionized water was carried out.
  • the electrodialyzer one having an effective area of 520 cm 2 ⁇ 5 pairs, was used.
  • demineralization was carried out by applying a voltage of 4 V per unit cell, whereby treated water having an electroconductivity of 0.08 ⁇ S/cm was constantly obtained at a production rate of 0.39 m 3 /hr.
  • the ion exchange membranes were taken out, and their state was inspected, whereby they were found to be pressed against the spacer nets without creasing, and their sizes immediately after being disassembled were 104% of the dried state in the case of the cation exchange membranes, and 103% of the dry state in the case of the anion exchange membranes. Thus, the dimensional change was found to be suppressed. Further, the ion exchange resins in the demineralizing compartments were taken out, and the volume was measured and found to be 123% of the volume of the demineralizing compartments.
  • Example 2 A test was carried out in the same manner as in Example 2 except that as an ion exchanger packed in the demineralizing compartments, the granular ion exchange resin mixture was used in a wet state. At the time of assembling the electrodialyzer, by the water of the ion exchange resins, the membranes in a dry state were swelled and underwent a dimensional change, whereby the membranes could not properly be set.
  • Example 2 A test was carried out in the same manner as in Example 1 except that concentrating compartment frames having a thickness of 1.6 mm were used without using spacer nets in the concentrating compartments.
  • the ion exchange membranes and the porous ion exchange sheets were thoroughly wetted by supplying water for 10 minutes and the pretreatment by conducting an electric current for 15 hours, and then a test for treating water was carried out, whereby there was no flowing out of concentrated water from the concentrating compartments, and it was impossible to carry out the operation. After the test, the ion exchange membranes were taken out, and their state was inspected, whereby the membranes were found to be pressed and deformed by the ion exchange sheets to close the concentrating compartments.
  • Example 2 A test was carried out in the same manner as in Example 2 except that the ion exchangers to be packed in the demineralizing compartments, were packed at a volume packing proportion of 45%.
  • the ion exchange membranes and the granular ion exchange resins were thoroughly wetted by supplying water for 10 minutes and the pretreatment by conducting an electric current for 15 hours, and then a test for treating water was carried out.
  • As the electrodialyzer one having an effective area of 520 cm 2 ⁇ 5 pairs, was employed.
  • demineralization was carried out by applying a voltage of 4 V per unit cell, whereby treated water having a low purity with an electroconductivity of 0.25 ⁇ S/cm, was obtained at a production rate of 0.35 m 3 /hr.
  • the ion exchange membranes were taken out, and their state was inspected, whereby they were found to be not pressed against the spacer nets and had many creases, and many pin holes were observed at the peaks of the creases.
  • Their sizes immediately after being disassembled were 112% of the dried state in the case of the cation exchange membranes and 110% of the dry state in the case of the anion exchange membranes. Thus, the dimensional change was found to be not substantially suppressed.
  • the granular ion exchange resins in the demineralizing compartments were taken out, and their volumes were measured and found to be 101% of the volumes of the demineralizing compartments.
  • ion exchange membranes can be set in a dry state in an electrodialyzer, and yet, the swelling deformation of membranes even after supplying water can be suppressed by bringing the ion exchange membranes in contact with the spacers by the pressure from the mineralizing compartment side, whereby mounting of the ion exchange membranes is simple. Further, there is a merit that formation of creases of the membranes due to the swelling deformation of the membranes can be avoided during the mounting or the subsequent supplying of water.
  • the handling efficiency is particularly excellent, whereby the costs can be reduced.

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  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
EP98103390A 1997-02-27 1998-02-26 Procédé d'assemblage d'un appareil pour la production d'eau desionisée Expired - Lifetime EP0862942B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP05860297A JP3644182B2 (ja) 1997-02-27 1997-02-27 脱イオン水の製造装置
JP58602/97 1997-02-27
JP5860297 1997-02-27

Publications (3)

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EP0862942A2 true EP0862942A2 (fr) 1998-09-09
EP0862942A3 EP0862942A3 (fr) 1998-10-07
EP0862942B1 EP0862942B1 (fr) 2002-09-18

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EP98103390A Expired - Lifetime EP0862942B1 (fr) 1997-02-27 1998-02-26 Procédé d'assemblage d'un appareil pour la production d'eau desionisée

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US (1) US6338784B1 (fr)
EP (1) EP0862942B1 (fr)
JP (1) JP3644182B2 (fr)
AT (1) ATE224227T1 (fr)
CA (1) CA2230629C (fr)
DE (1) DE69807959T2 (fr)

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MXPA02000037A (es) * 1999-06-21 2003-01-28 E Cell Corp Membrana de intercambio ionico heterogenea y metodo de manufactura de la misma.
CA2353617A1 (fr) * 2000-07-24 2002-01-24 Asahi Glass Company, Limited Matiere echangeuse d'anions heterogene
CA2413467A1 (fr) * 2002-11-29 2004-05-29 Ian Glenn Towe Piece d'ecartement de membranes a commande electrique d'un appareil de traitement
US7288176B2 (en) * 2003-04-23 2007-10-30 Dionex Corporation Method and apparatus for generating high purity eluant
US9283510B2 (en) 2011-08-22 2016-03-15 The Trustees Of Columbia University In The City Of New York Method for producing a moisture swing sorbent for carbon dioxide capture from air
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GB201403553D0 (en) * 2014-02-28 2014-04-16 Fujifilm Mfg Europe Bv Membrane stacks
CN104016451B (zh) * 2014-06-24 2015-08-26 上海理工大学 压力场与电场协同作用双膜脱盐的设备和应用方法
JP7086694B2 (ja) * 2018-04-20 2022-06-20 株式会社ディスコ 凝集剤、フィルター及び廃液処理方法
CN115180693A (zh) * 2022-07-11 2022-10-14 重庆钢铁股份有限公司 一种用于凝结水精处理的连续电除盐系统

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GB893051A (en) * 1959-04-30 1962-04-04 John Thompson Kennicott Ltd Improvements in or relating to an electrodialysis apparatus
GB942762A (en) * 1960-05-13 1963-11-27 John Thompson Kennicott Ltd A method of packing a receptacle with comminuted material
EP0170895B1 (fr) * 1984-07-09 1989-03-22 Millipore Corporation Appareil et procédé d'électrodésionisation
US4804451A (en) * 1986-10-01 1989-02-14 Millipore Corporation Depletion compartment for deionization apparatus and method
WO1995032052A1 (fr) * 1994-05-20 1995-11-30 U.S. Filter/Ionpure, Inc. Appareil et procede d'electrodesionisation par inversion simple ou double de polarite
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EP2402290A1 (fr) * 2010-07-01 2012-01-04 Millipore Corporation Dispositif d'électro-désionisation et procédé comprenant le contrôle du courant électrique par la mesure de l'expansion du matériau d'échange d'ions
US8480873B2 (en) 2010-07-01 2013-07-09 Emd Millipore Corporation Electrodeionization device and method comprising control of the electric current by measurement of ion-exchange material expansion
CN103787470A (zh) * 2010-07-01 2014-05-14 Emd密理博公司 包括通过测量离子交换物质膨胀进行电流控制的去离子装置和方法
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NL2011331C2 (en) * 2013-08-23 2015-02-24 Stichting Wetsus Ct Excellence Sustainable Water T Device and method for performing an ion-exchange process.
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Also Published As

Publication number Publication date
CA2230629C (fr) 2006-10-17
US6338784B1 (en) 2002-01-15
DE69807959D1 (de) 2002-10-24
CA2230629A1 (fr) 1998-08-27
JPH10235158A (ja) 1998-09-08
JP3644182B2 (ja) 2005-04-27
DE69807959T2 (de) 2003-05-22
ATE224227T1 (de) 2002-10-15
EP0862942B1 (fr) 2002-09-18
EP0862942A3 (fr) 1998-10-07

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